Size classified cereal starch granules

ABSTRACT

A wet process for separating certain cereal starch granules according to size, and the large granule cereal starch made thereby. Barley, rye and wheat starch may be treated in the process, and may be subjected to further modifications, such as cross-linking, to further improve the properties of the product.

United States Patent 1191 Bond et al. 1 Aug. 26, 1975 [54] SIZE CLASSIFIED CEREAL STARCH 2,817,441 12/1957 Leeman 209/211 GRANULES 2,819,795 1/1958 209 211 2,829,771 4/1958 209/211 [75] Inventors: John L. Bond, Dublm; Saul Rogols, 3 16 49 1/19 5 209/211 Circleville; John W. Salter, 3,479,220 1 H1969 Ferrara 127/38 westervllle, all of 01110 OTHER PUBLICATIONS Assignefil Staley Manufacturing Chemical Abstracts, 53:8463i 1959 p y Decatur Chemical Abstracts, 56:13304d (1962). [22] Filed, June 12, 1974 Methods in Carbohydrate Chem., R. L. Whistler,

Appl. No.: 478,564

Related U.S. Application Data [63] Continuation of Ser. No. 180,588, Sept. 15, 1971,

abandoned,

[52] U.S. Cl. 127/32; 117/362; 117/100 A; 127/33; 127/69; 127/70; 127/71; 209/211; 426/152 [51] Int. Cl. C13L l/08 [58] Field of Search 127/32, 70, 71, 67, 69, 127/38, 33; 209/211; 117/362 [56] References Cited UNITED STATES PATENTS 2,343,048 2/1944 Eblc 127/70 2,642,185 6/1953 Fontein 209/21] Ed., Vol. IV, 20-24, Academic Press, New York, 1964.

Primary Examiner-Morris O. Wolk Assistant Examiner-Sidney Marantz Attorney, Agent, or Firm-Howard J. Barnett; Charles .1. Meyerson [57] ABSTRACT A wet process for separating certain cereal starch granules according to size, and the large granule cereal starch made thereby. Barley, rye and wheat starch may be treated in the process, and may be subjected to further modifications, such as cross-linking, to further improve the properties of the product.

28 Claims, 9 Drawing Figures pmmmmszslars 3,901,725

sum 1 OF 3 FIGURE 1 FIGURE 2 FIGURE 3 FIGURE 4 IN V EN TORS ATT RNEY PATENTEU M1626 191s SHEET 2 BF 3 w mmawE N MEDOE m mmnol M wfi MgM ATTORNEY Pmmenmczsms sum 3 0r 3 w mmzoI :3 $5525 M3253.

i O m i O O m m mmDwE %,RM {Emmi M w YLAMJJER INVENTORS I a l M M ATTORNEY CON -OOm OO oom OOK. -OOm OOm OOO SIZE CLASSIFIED CEREAL STARCH GRANULES This application is a continuation of US. Patent application Ser. No. 180.588. entitled Size Classified Cereal Starch Granules filed on Sept. 15. l97l. now abandoned.

Native colloid, prime grade wheat starch slurry is pumped through a series of cyclone-type separators in a wet process system to separate the large granule por tion from the small granule portion. These small granules range in size from about 340 microns.

A recirculation system is provided to get a starch granule fraction comprising 99 percent by weight large granules ranging in size from about l2 microns to 40 microns. and at least 22 percent comprising granules which are 22 microns or larger in size. This product has a very large portion of large granules in comparison to prime grade wheat. which normally comprises about 2.5 percent granules which are 22 microns or larger. The uniformly sized large starch granules derived by the separation process are particularly useful in antioffset lithograph powders. and as protective particles in the sensitized surface coating of non-carbon duplicating paper which normally contains microencapsulated ink. In the latter application. the uniform sized cereal starch particles replace scarce arrowroot starch particles to prevent premature rupture of the ink-containing capsules during handling of the sensitized paper. There is also evidence to show an improvement in baked goods attributable to the use of reconstituted flours incorporating the large granule starch obtained The smaller. uniformly sized starch granules also have more uses because of their uniform smaller size. particularly as a substitute for rice starch. Wheat, bar ley and rye starch are suitable base starch materials because they are easily separated into small and large particle fractions. Wheat is the most readily available of these cereal grains. and is therefore the presently preferred base starch.

BACKGROUND OF THE INVENTION This invention provides a new means for expanding the possible uses of certain cereal starches. particularly wheat starch. and makes use of their generally spheroidal granule form. A wet process separation is used to obtain starch granules of uniform size which are useful in a wider range of applications. In particular. this product is used as a substitute for the more expensive and exotic root starch. arrowroot. In addition. the small granule cereal starch by-product which results from the separation process may be used as a rice starch substitute. and to improve the texture of certain bakery products in which a fine-grain texture is desirable.

DESCRIPTION OF THE PRIOR ART In the past. some attempts have been made to separate wheat starch granules according to size. but such separation techniques were usually accomplished by air classification of the initial flour. or otherwise effected on the total wheat starch in the dry state. One such method has been described by J. W. Knight. in his work entitled. The Chemistry of Wheat Starch & Gluten. published by Leonard Hill. London. (I965). According to Knight. the dry separation is only partially successful. Also. Anderson and Griffin have published a method for separating gluten and starch from flour, but no mention is made here ofa wet-process separation of the 2 wheat starch granules according to size (Anderson, R. A.. and Griffin. E. L.. Die Slarke. 6 (l4), pp. 2 l0-2l2. 1962)).

Hoseny et al. made use of a screening technique to obtain a small granule wheat starch fraction for testing at the Hard Winter Wheat Laboratory. Manhattan, Kansas (Cereal Chemistry. 48:l9l20l. l97l). They observed no change in gelatinization temperature when comparing prime grade wheat (mixed granule sizes) to small granule wheat. The performances of these samples in breadmaking was also judged to be the same. so it was concluded that granule size did not govern the breadmaking potential of a wheat starch. Sollars. et al.. however. speculated that starch granule size does play a dominating role in performance of reconstituted flours in baking (See Sollars et al.. Wheat and Starch in Flour. Cereal Chemistry 48:397-410. l97l page 408). The method used by Hoseny et al. to obtain his small granule wheat starch incorporated a screening technique which apparently produced a combination of small granule starch particles. fragmented particles. and pentosans. No size is stated, but it would appear from Hoseny et al.s photomicrographs that a certain amount of larger granule particles did find their way into the product (Ibid: FIG. I. SGW. page I96).

In a recent collection work edited by Y. Pomcranz, entitled, WHEAT: Chemistry and Technology. published by The American Assn. Cereal Chemists, St. Paul. Minn. (I971), [Chapter 7, Carbohydrates, authored by B. L. dAppolonia and K. A. Gilles, pp. 332. 336. 344]. the microscopic appearance of wheat starch granules was described in detail. The presence of two strikingly different granule types was noted: large "lenticular granules most with a diameter of 20 to 35 microns; and small spherical granules with diameters largely in the range of 2 to ID microns. It was also there reported that the larger granules in wheat starch. although representing only 12.5 percent ofthe total numher, account for most of the weight and the larger portion of the surface. Reporting on the physical properties of wheat starch. the author reported that swelling of granules and loss of birefringence was observed to occur in larger granules first. The gelatinization of this wheat starch was observed to occur over a range of temperatures.

F. J. Fontein described a method of refining a starch suspension in US. Pat. No. 2,642,185, issued June 16. 1953. Although on the surface his method appears somewhat similar to applicants. there are some significant differences. For example. Fontein is only interested in obtaining starch granules which are less than seven microns in size. The starch granules which are larger are apparently withdrawn and subjected to further processing. Those granules which are about 20 microns in size and larger are the very ones which applicants find most important as a commercial product. The smaller particles below 12 microns in size are merely a useful byproduct of applicants separation system.

Fonteins process uses a cyclone separation system in which the starch granules below seven microns are collected and then further refined to remove substantially all the more coarse particles. The whole object of the Fontein method is to obtain a refined starch having uniform granules less than ten microns in size. and preferably smaller than seven microns.

Fonteins circulation system takes the overflow from the top, or base aperture. of his hydrocyclone. and

3 feeds this to a second hydrocyclone. The overflow from the top (base) aperture of the second hydrocyclone is collected as a fine granule product (smaller than seven microns).

Applicants method, in contrast, requires that the input into their first hydrocyclone be a prime grade, washed wheat starch slurry at a very specific viscosity level. The underflow, from the apex opening of this first hydrocyclone is collected and fed as the feed into a second hydrocyclone, so that the feed to the second hydrocyclone is primarily a large granule. partially separated starch slurry. The viscosity level is again adjusted very carefully before the underflow is fed into the second hydrocyclone. The desired product is the underflow from the second hydrocyclone.

The initial input into the system of the invention is prime grade, washed wheat starch slurry, so the overflow fractions are also quite uniform in size, having a particle size ranging from about 3-l2 microns. This overflow fraction is also collected in each instance, and can be used in those applications where a small granule cereal starch is used. This small granule by-product may be used as a substitute for small granule rice starch, for example.

The process of the invention produces an extremely good large granule starch product which is particularly suited for use as a protective particle in a surface coating for carbonless duplicating paper, and which has certain desirable physical characteristics which distinguish it from the small granule product. The large granule product may be further modified to enhance its desirable properties. For example, its heat stability may be improved by some cross-linking, as more fully set forth below,

U.S. Pat. No. 2,504,962 describes a process for separating starch from flour by means of a series of screens. However. no mention is made here of wet process separation of starch granules according to size. U.S. Pat. No. 3,489,605 issued Jan. 13, I970 describes an apparatus for gluten separation from starch. Again, the object is to remove starch in toto without any attempt to classify the starch granules according to size. U.S. Pat. No. 3,354,046 issued Nov. 21, I967 describes the use of chemicals or enzymes as an aid in the filtration of starch products.

Dutch Patent Specification No. 7005045, opened for public inspection Oct. 12, 1970 (based on U.S. Ser. No. 814,336. filed Apr. 8, 1969) describes a pressure sensitive coating on a duplicating paper. The coating includes microencapsulated ink particles which, when ruptured by the pressure of an image writing instrument, will transfer a duplicate image to an adjacent paper surface.

Such specially coated paper requires a protective material having a relatively uniform microparticle size slightly larger than the encapsulated ink particles to prevent the premature rupture of the ink containing microcapsulcs in the paper coating during storage or handling of the coated paper. The specification discloses various starch particles as canditates for the protective material, and states that arrowroot starch granules are preferred because of their uniform relatively large granule size in the order of 50 microns.

Wheat starch granules were not rated as well as arrowroot because the granules range in size from 235 microns. Barley and rye were not even listed or rated in the subject Ducth specification. No advantage was ap- 4 parently seen in either a thermal or chemical treatment for the disclosed protective starch granules.

In summary. one would conclude that the best protective material for pressure sensitive duplicating paper is native arrowroot starch granules. and that wheat starch would be fourth choice, after potato and sage. Obtaining a sufficient supply of arrowroot starch presents a serious obstacle. because it is obtained primarily from the root of a plant (Maranla urundinut'eu) grown on the island of St. Vincent in the West Indies. The arrowroot starch so produced is used mostly in specialty foods for children invalids, and is relatively expensive.

There is, therefore. a definite need for a less expensive protective material for pressure sensitive duplicat ing paper. The material should meet all the requirements set forth above. and should be a material which is relatively plentiful. To the best of applicants knowledge, no prior efforts have been made to obtain a uniform, large granule starch product from a prime grade cereal starch slurry such as wheat, barley or rye, particularly with the goal in mind to obtain a product having 99% by weight of the granules ranging in size from l2-40 microns, and at least 22 percent of the granules about 22 microns in size. or larger.

The very recent collection work mentioned above (Wheat: Chemistry and Technology) describes the effects to be obtained by intermolecular bonding of starch granules (p. 344). However, there is no mention here of any difference if the granules have been first size classified. The main observed effect was apparently inhibition of granule swelling. and prevention of breakdown of the gelatinized pastes made from such cross-linked starch granules. The extent of crosslinking suggested here is in the order of about one cross link per 2,000 glucose units.

The use of the hydrocyclone separator has been described more recently in the literature, and in patents other than Fontein, U.S. Pat. No. 2,642,!85, but it is believed that the device has never been used before in a system having a flow pattern such as that of the sub ject invention with the purpose of separating and saving a large granule, prime grade starch, relatively free of impurities, which is particularly useful as a protective material in pressure sensitive microencapsulated paper coatings. U.S. Pat. No. 3,25 l,7l7, Honeychureh et al.. issued May 17, 1966 on an application filed Oct. 15, I962. discloses the use of hydrocyclones in combina tion with centrifuges to remove soluble material in a mill stream thickening step in a cornstarch wet milling process. There is no intent or suggestion here that the starch granules be also separated according to size. In Whistler et al., Op. Cit, Vol. ll, p. 42, the hydroeyclone separation is also described, but the purpose is to separate heavier endosperm and fiber particles from the lighter germ containing starch. The germ is then washed to remove starch, with no attempt being made to further separate the starch granules according to size.

In summary, the object of most of the prior art has been to improve the existing methods of separating starch from the gluten and fibers of the raw grain kernels. For wheat wet milling. the most widely practiced method has been to first form a dough of wheat flour plus water in the correct proportions to produce a wet gluten which is typically ductile, tenacious and elastic. The wet gluten is then formed into a dough, and the starch separation of the gluten from all the starch without regard to granule size is effected. The Fontein patent mentioned above goes a step further and collects uniformly small starch particles less than ten microns in size. but ignores the large size particles.

SUMMARY OF THE INVENTION Applicants invention is directed to a specially processed cereal starch comprising starch granules in which 99 percent by weight of the product comprises starch granules above [2 microns in size and at least 22 percent of these granules are larger than 22 microns. The invention is also directed to the wet process separation of starch granules to obtain this large granule starch. A series of hydrocyclone separators are used in combination with a centrifugal separator to effectively separate a native colloid prime grade cereal starch slurry into two distinct portions to obtain separate granule size classifications. It is important to the success of the system that the method be performed on prime grade starch slurry which has not been subjected to a drying step. and then reslurried. The system ob tains all the advantages of a wet process system. and starch granule separation into two uniform size classifications is obtained. Approximarely 99% by weight of the starch granules 12 microns or over are separated from the smaller granule sizes. and about 55 percent by weight of these larger granules comprise which are 22 microns, or larger.

The possible uses for wheat starch is significantly increased by the provision of a large granulespecial wheat starch. This new starch is particularly useful as a replacement for the relatively scarce and expensive arrowroot starch used as a protective material in coated carbonless copy paper which are micro-encapsulated ink to form copy images. The new large granule wheat starch can also be used to replace arrowroot starch granules in an antioffset lithographic powder. which is spread or sprayed on freshly lithographed paper sheets to permit stacking without image blurring or transfer.

DETAILED DESCRIPTION OF THE INVENTION The drawings serve to illustrate the invention more fully.

FIG. I ofthe drawings is a sketch made from a photomicrograph enlarged IOOX showing typical arrowroot starch granules;

FIG. 2 is a sketch made from a photomicrograph enlarged lOOX showing typical prime grade wheat starch granules and contains starch granules ranging in size from 3 to 40 microns;

FIG. 3 is a sketch made from a photomicrograph enlarged IUUX showing the concentrated small granule starch fraction in which most of the particles are less than 12 microns;

FIG. 4 is a sketch made from a photomicrograph enlarged IOOX and shows the large granule wheat starch of the invention:

FIG. 5 is a sketch made from a photomicrograph enlarged IOUX of the large granule wheat starch after being heated at 90C. for 40 minutes;

FIG. 6 is a sketch made from a photomicrograph enlarged |()()X showing a sample of urea-formaldehyde cross-linked large granule wheat starch after heating at 90C. for 40 minutes:

FIG. 7 is a general schematic diagram showing the process steps to obtain the starch products ofthe invenlion;

FIG. 8 is a graph comparing particle size distribution of arrowroot starch with ordinary prime grade wheat 6 starch and with the special large granule wheat starch of the invention; and

FIG. 9 is a graph comparing the effect of heating on the viscosity of wheat starch slurries of prime grade wheat starch and the small granule wheat starch and the large granule wheat starch of the invention.

The most striking point to be noted in the drawings. particularly FIGS. 1 and 4, is that the large granule wheat starch obtained by the invention is very similar in shape and size to the much more scarce native arrowroot starch. In fact. the large granule wheat starch particles shown in FIG. 4 appear to be more spheroid than arrowroot. When the product is to be used as a protective particulate coating for microencapsulated ink coated papers. it is believed that the spheroid granule shape of the large wheat granules makes the product particularly effective.

Dutch Patent specification No. /05045 filed Apr. 8. [970. based on US. Pat. application Ser. No. 8I4,336. filed Apr. 8. I969 is directed to a specially coated paper which responds to typing pressure to produce an image on a second. underlayer copy paper. Chromogenic ink capsules are coated on the back of the paper to receive the original typed or written impressed numbers or letters, or other symbols. When these ehromogenic ink capsules are ruptured. they re lease and transfer the image to the specially treated front surface of the copy paper. and an accurate copy of the topsheet is obtained.

This specially treated paper requires a protective material in the coating which includes the microencapsulated ink to prevent premature rupture of the pressure sensitive capsules during handling. The subject Dutch specification teaches the use of starch particles. particularly arrowroot. because it has granules of uniform large size. Examples using corn. wheat. and potato starch are given. but it is clear from a full reading of the disclosure that the more effective starch particles are arrowroot. Commercially. the other starches mentioned are not even used. A serious problem exists in producing the pressure sensitive copy paper described in the subject application because of the world wide shortage of arrowroot starch. The shortage is so critical that applicants assignee has sponsored trips to the island areas in the Carribean where arrowroot is grown in an attempt to convince the landowners there to grow arrowroot for special uses. Wheat starch. on the other hand. is relatively plentiful. and can provide an economical and readily available replacement for arrowroot if the desirable properties of arrowroot starch can be duplicated or surpassed.

Others have attempted to separate previously dried wheat starch into a large granule portion and a small granule portion using wet processing and centrifugal separators. These attempts were unsuccessful. apparently because of some effect on the prime grade wheat starch caused by the drying process.

Applicants discovered unexpectedly that it is possible to separate a large granule wheat starch from original prime grade. native colloid mixed granule size wheat starch slurry which has not been dried. Such a slurry is a native colloid. having resulted directly from the actual wheat starch wet milling process before any drying step. It has been found that to be successful. applicants separation process must have an input stream which is purified native colloid prime grade wheat starch. as nearly free of the air. fiber and gluten as possible. This is of great importance. because foreign materials such 7 as salt. fiber and gluten can prevent the cyclone separator from functioning properly to provide a large granulc starch portion, A

Another important consideration to obtain a large granule wheat starch which is a match" for arrowroot starch is the requirement of having at least two cyclone separators in series so that the underflow from the first cyclone separator provides the feed to the second cyclone separator. The viscosity of the input slurry to both cyclone separators should be carefully adjusted within narrow limits to insure the correct functioning of the cyclone separators. This arrangement has been found to be necessary to obtain approximately the same percentage concentration of large wheat starch granules as is normally found in the much scarcer arrowroot starch.

Native wheat starch is relatively plentiful, and has a wide range in granule size, from 2 to about 35 microns. Most of the granules fall at the upper and lower ends of the size range, with very few intermediate sized granules, so that wheat starch becomes a natural canditate for separation of the starch granules according to size. It is also contemplated that native rye and barley starch can be separated into a large granule portion and a small granule portion using the teachings of the invention.

FIG. 8 of the attached drawings is a graphic illustration of particle size distribution by weight, and compares the particles size distribution in a typical, prime grade wheat, Sample A, with an arrowroot starch, Sample B, and the large granule wheat starch of the invention, Sample C. Most striking in FIG. 8 is the almost identical particle size distribution exhibited by Sample C, applicants new large granule wheat starch, with that of Sample B, the extremely scarce and expensive arrowroot starch.

The darmatic improvement attained in particle size distribution by applicants new large granule wheat starch over typical prime grade wheat starch can be readily appreciated when the curve for Sample A is compared to the curve for Sample C. Sample A contained only about 2I percent by weight of starch granules which were 22 microns, or larger, whereas Sample C contained more than 55 percent by weight 22 micron starch granules, or larger.

The particle size distribution analyses were obtained by the use of a Coulter Counter, following the procedures generally outlined in the Instruction Manual for Coulter Company Industrial Model A. The Coulter Counter and Instruction Manual were obtained from Coulter Electronics Industrial Division, 2525 N. Sheffield Ave., Chicago, Ill., and this equipment and its operation are described in US. Pat. Nos. 2,656,508, 2,869,078, 2,985,830 and 3,0I5,775 as well as other publications.

The Coulter Counter determines the number and size of particles suspended in an electrically conductive liquid by forcing the suspension to flow through a small aperture having an immersed electrode on each side thereof. As a particle passes through the aperture, it changes the resistance between the electrodes. producing a voltage pulse of a magnitude proportional to the particle volume. The series of pulses so produced is electronically scaled and counted. and this data is analyzed to produce the information for the particle size distribution graphs for each sample. and which are set forth compositcly in FIG. 8 of the drawings.

'l he Instruction Manual lis'ts particular apparatus for use with the Coulter Counter. Model A. For the subject measurements. the aperture used vtas l4ll microns. .A gain setting of 6 was used. A two-spaced Waring Blendor with a scmi-micro container (Ccnco 172462) was used, along with the following equipment:

a. filter holder (Milliporc XXII) 047 00);

b. filters, 0.45 micron (Millipore HAWP 047 ()0);

c. I ml. electrolytic bcakcrs (LaPinc 20-8I d. stirrer, air-driven (A. H. Thomas 9224) with glass stirring rod. to replace the electric stirrer;

e. Voltmeter. Triplett Elec. Instrument Company,

Bluffton, Ohio. Model 625-NA.

The reagents used include a first reagent comprising 2% sodium chloride solution which comprises 40 grams NaCl and 2 ml of 37% formaldehyde in sufficient distilled water to make 2 liters of solution. This first rca gent provides the electrolyte conducting media in which the particles to be observed are suspended. The second reagent used is Triton X-IOO, a wetting agent made by Rohm & Haas. and is used to keep the particles suspended during actual counting of a sample.

To calibrate the equipment to insure an accurate count, and to identify starch particles accurately according to size, ragweed pollen was used, and the general calibration procedure as set forth in the Coulter Counter Instruction Manual was followed. Ragwood pollen was chosen for the calibration step because these particles are quite uniforn in size, and average about 20 microns, which is about in the middle of the size range which was to be measured for the preparation of FIG. 8 of the drawings. lsopropanol was used to wet the ragweed pollen prior to mixing the sample with the electrolyte solution. In the actual counting runs, Triton X400 was used to maintain thorough dispersion of the starch granules after first dispersing the sample in the electrolyte. During calibration, the ragweed pollen must be handled carefully, considering possible allergy problems.

Procedures are set forth in the Instruction Manual for analyzing the Coulter Counter data, and the raw data can be readily adapted to computer program sorting and analysis, so that an extremely accurate count of particles can be made in a particular sample, along with an accurate characterization of these particles by size.

Coulter Counter analysis of large granule starch samples made according to the general method of the in vention has made possible a very specific degree of adjustment in the process parameters to obtain a large granule product of consistently good quality. Particular starch samples can be analyzed with the Coulter Counter and appropriate computer programs to deter mine whether the sample has the required number of large particles in excess of 22 microns in size.

The large granule starch product of the invention can be subjected to further modifications, such as etherification, esterification, enzyme hydrolysis, and crosslinking, and to any combination of these. In certain applications, where a lower viscosity product is desired, the large granule starch may be oxidized, and also modified as described if additional changes are desired. A hydrochloric acid-modified, epichlorohydrin cross- Iinkcd product exhibited increased heat stability. the passing temperature being raised about 61C.

BRABENDER AMYLOGRAPH COMPARISONS The large granule wheat starch product has been compared to prime grade whcat starch and to the small 9 granule wheat starch by-product for viscosity charac teristics. llie results of this comparison are illustrated graphicall in H0. 9 of the drawings. Three slurry Samples. A. C and D. were prepared. each having 8 percent solids. dry substance basis. Each sample was subjected to the same conditions and the respective viscosity behaviors were measured during heating. holding at a constant temperature. and during cooling for the time periods and at the temperatures and rates indicated in FIG. 9.

The prime grade native wheat starch. Sample A. containing a normal mixture of both large and small starch granules. rose in viscosity during heating up to about 200 Brabcnder Units (B.U.J. but did not increase further in viscosity until cooling was commenced at sixty minutes into the test. Viscosity for Sample A then rises at a constant rate to a maximum of about 770 B.U. at about 96.5 minutes into the run. or after about 36.5 minutes of cooling. The temperature of the sample at this point has been lowered to about 40C.

The small granule starch. Sample D. which was collected as a by-product from the method of the invention. exhibited an interesting and somewhat better viscosity behavoir under the same test conditions. After about 34.5 minutes heating, viscosity reached a level of about 280 EU. When the sample was held at 95C. for approximately the next 25 minutes. viscosity decreased very gradually to about 225 B.U.. and upon cooling, Sample D quickly increased to a viscosity of 655 EU. after only fifteen minutes cooling, and thereafter, the viscosity steadily increased to about 1.070 B.U. at the end of the cooling period. or 96.5 minutes into the run.

The large granule strach, Sample C. made according to the invention. performed very similarly to Sample D during the last twenty minutes of cooling. it reached a higher viscosity level sooner than either Sample D or A. and maintained a higher level than either Sample D or A throughout the test. After the initial heating period. and at forty minutes into the test. Sample C had already reached a viscosity of about 375 B.U.. and never dropped below this level. During the "hold period at 95C.. the viscosity of Sample C continued to increase slightly to 390 EU. at sixty minutes into the run. When Sample C was cooled. it commenced a very regular rate of increase in viscosity up to about l.lO B.U. at the end of the test run.

The comparisons illustrated in FIG. 9 definitely show an improved viscosity performance not only for the small granule starch by-product of the invention. but especially for the large granule product. Ordinarly prime grade wheat starch. containing both large and small starch granules in the normal amounts and proportions never attained a viscosity more than 800 EU. during the tests. while both the small granule starch and the large granule starch made according to the invention attained viscosities in excess of 1.000 B.U.

CROSS-LINKED PRODUCT Additional improvements in the large granule product ofthe invention can be obtained by further modification of the starch. FIGS. and 6 ofthe drawings illus trate dramatically the striking improvement obtained by cross-linking the large granule starch with urea formaldehyde. FIG. 5 shows the effect on the starch granules caused by heating the product at 90C for 40 minutes. It can be seen that the granules have fragmented. and are no longer intact. The granules shown in FIG. 6. which have been cross-linked with ureaformaldehyde. are intact and homogeneous. with well defined "roundncss. The sample in FIG. 6 has been subjected to the identical heating conditions of C. for 40 minutes it is clear from the illustrated results of these tests that the particular modification to the large granule product effected by crosslinking substantially improved its heat resistance. making the product even more useful in those carbonless duplicating paper coating processes which are performed at elevated temperatures.

These same samples were observed under a Kofler Hot Stage microscope to determine the temperature at which I00 percent of the granules lose birefringence. The samples were also observed for gelatinization point using an amylograph. The gelatinization point temperature recorded was that temperature at which the gran ules began to paste. thereby increasing Brabender viscosity. The following data was recorded:

The small degree of urea formaldehyde cross-linking used raised the gelatinization point temperature 6C.. as observed on the Kofler Hot Stage microscope. The amylograph comparison was even more dramatic. The large granule sample which had not been subjected to cross-linking showed evidence of pasting at a temperature of 8285C. The cross-linked product showed no evidence of pasting when subjected to the same conditions.

it is contemplated that other cross-linking reagents. such as epichlorohydrin. acetaldehyde. ureaformaldehyde in ratios ranging from 30-50 percent by weight of urea to 30-50 percent formaldehyde. could also be used. Best results were obtained. however. using a urea-formaldehyde-water reagent mixture of the ratio (29:59:15). This latter reagent mixture proved most adaptable to the manufacturing process. and is the easiest to handle. lt is available from E. l. duPont, lnc., designated as UF 85.

The amount of cross-linking was controlled by monitoring the alkali fluidity of the reaction mixture containing the cross-linking agent and starch dispersion. and by neutralizing with sulfuric acid as soon as an alkali fluidity range from about 4976 ml. measured on a 2.5 gm. starch d.s.b.. in a ml. solution is obtained. The presently preferred alkali fluidity on a 2.5 gm. sample is about 59. The reaction is stopped at this point. since it has been found that this particular degree of crosslinking will inhibit the starch product sufficiently to give sufficient heat stability to the cross-linked granules for them to retain their shape at the elevated tcm perature required during the carbonless paper coating process.

The alkali fluidity test referred to immediately above is presently considered the most convenient means of controlling the degree of cross-linking. The test is generally described in US. Pat. No. 3.238.l93 at columns 7 and 8, lines 40-61 and 1-9. respectively. The concentration of the alkali starch dispersion for a particular test sample is determined by adding 90 ml. of 0.25 N sodium hydroxide to a slurry of neutralized. filtered.

water-Mashed wet starch cake containing 2.5 grams of the cross-linked starch derivative. dry solids basis (d.s.b. The starch sample is slurried in water to make 10 ml. of total water prior to the addition of 90 ml. of 0.25 N sodium hydroxide. After mixing the starch slurry with the sodium hydroxide solution. the suspension is stirred at between 450 and 460 rpm. for three minutes in order to paste the starch. The resulting starch solution is poured into a fluidity funnel having a specific water time between about 30 and 40 seconds. The number of ml. of starch solution which flows through the funnel in the water-time" (defined below) is the alkali fluidity of the starch. The extent of crosslinking is monitored by repeating the above test at regular intervals with samples taken from the reaction mixture. When the alkali fluidity test is within the desired range. the cross-linking reaction is stopped.

The fluidity funnel used for the alkali fluidity tests described herein comprises two main parts. a funnel body and a funnel tip thrcadably attached thereto. A simple plunger-type. tapered valve on a glass stem can be used to manually control flow through the funnel orifice. The funnel parts are precision-machined from stainless steel stock, and polished to very smooth surfaces on all parts which come in contact with the test samples.

The funnel body defines a generally cone shaped vessel having a sixty degree angle (or taper) between opposite. converging funnel walls. Funnel body height is sufficient to hold at least a I ml. sample. and a 0.277 inch orifice and fluid passage is provided at the narrowest portion of the funnel for attachment to the funnel tip. The fluid passage is 1 inches in length from the orifice to the narrow end of the funnel body. The oppo site. wide orifice of the funnel body is oriented upwardly, and the tapered valve is inserted downwardly from above into the smaller orifice during the tests. Operation of this valve against the watcrtirne" of the funnel gives the test readings. The funnel tip is a cup shaped member. which is threadably received on the narrow end of the funnel body. The internal chamber of the funnel tip is hemispherical and has a 3/16 inch diameter with a lower central opening of 0.070 inch which is 0.0492 inches in length. The total height for the lower end of the funnel body passage to the lower external orifice of the funnel tip includes the height of the ball chamber (0. I008 inches) and the length (0.0492 inches) of the funnel tip opening.

The composite apparatus described above is vertically disposed above a graduated cylinder for the actual tests. At the beginning of each test. the water-time for the apparatus is checked by running I00 ml. of pure water through the funnel and recording the total elapsed time. The water time then becomes the time against which each sample is tested.

The flow through the funnel during the water-time is measured in milliliters and recorded after each test. The funnel is thoroughly washed between each test to avoid irregular observations. Other starch concentrations may be used. as indicated. for the tests. For example. in some instances it is desirable to use a 5 or g. dry substance basis sample. In such cases. 0.375 N sodium hydroxice is used. Otherwise the equipment and the procedure is the same.

The large granule starch and cross-linked large gran ule starch of the invention both exhibited subsieve values considerably higher than prime grade and compa rably cross'linked prime grade wheat starch. as is shown below:

Sul Slew alue russ ltlthcd. prune grade \thcal starch it] 1 The equipment used to obtain the above sub-sieve values was a Fisher Model Sub-Sieve Sizer. available from Fisher Scientific Co.. Inc.. Instrument Division. Pittsburgh, Pa. When operated according to the in' structions supplied. this instrument provides quick and reproducible measurements ofaverage particle sizes in the 0.2 to 50 micron range (Fisher Instruction Manual. Instrument Division. Catalog Number 14-311). Each measurement is read directly from the curve on the Calculator Chart located at the top half of the instrument. Air permeability is measured and converted to average particle size. based on the principle that air flows more readily through a bed of coarse powder than through an otherwise equal bed of fine powder that is equal in shape of bed, apparent volume. and percentage of voids. Measurements of average particle size are obtained by reason of difference in general coarscness of material. that is, differences in average pore diameter and total interstitial surface. Although based on complex formulas, the standardization of conditions by Ernest L. Gooden and Charles M. Smith have made it possible to obtain a direct reading of average particle size of a sample from the instrument without mathematical computation, Gooden. E. L. & Smith. Charles M., Industrial Engineering Chemistry Analytical Edition l2z479-482 (1940).

COMPARATIVE ANALYSIS The large and small granule products made according to the invention were compared to prime grade wheat starch for protein. ash. water solubles. film and fat content with the following results:

tether extraction only) The above analyses show most clearly that the protein content of the prime grade wheat starch is primarily with the small granule portion. The protein content of the small granule fraction is more than double that of prime grade wheat. whereas the protein content of the large granule fraction is only about 60 percent of that for prime grade wheat. Ash content of the prime grade wheat is more than one and one-half times that of the large granule starch product of the invention.

Most notable in this analysis was the complete absence of detectable water soluble carbohydrates from the large granule starch product of the invention. The

I3 cthcr extracted fat content of the large granule starch was only ll.(ll per cent as compared to 0.17 and (H8 percent. respectively. for the small granule starch and prime grade wheat starch samples.

OXIDATION EFFECT COMPARATIVE TESTS In another comparison. prime grade wheat starch. large granule wheat starch and small granule wheat starch were all slurried and then oxidized by the following methods to compare oxidation ability of each as starting materials for routine products. The oxidation procedures used were as set forth below:

Addition of NaOCl at 3% level (Ch/Starch) l) Low pH: Slurry (7g! pH 2.5-3.0

Viscosity measurements were carried out on the above samples using an Ostwald-Fenske Viscometer. Model 200. with a constant speed stirrer adjusted to IOU-200 RPM. A constant temperature water bath of40C.. plus or minus 1C. was used. All reagents and glassware are also stabilized at the same temperature. A stopwatch having 0.1 second graduations is used for timing the tests. A 0.50 N NaOH solution is used to make up the starch-alkali suspensions to be tested The test procedure used was generally as follows:

I. The six samples to he tested (3 low pH and 3 high pH) were all first weighed to make up 7 g. dry basis. in each sample;

2. The sample was then placed in a 250 ml beaker;

3. l mls. of distilled water was added to the beaker and stirred until water-starch paste was completely smooth;

. The beaker was then placed in water bath at 40C. and agitated with constant speed stirrer at 100-200 RPM;

. 9t) mls of ().5N NaOH was added. and the stopwatch was started;

. The starch-alkali suspension was stirred until completely lump free for a period ranging from 3-7 minutes;

Then 10 oils of the lump free starch-alkali suspension is transferred from the sample to the Ostwald- Fenske viscometer using a l0 ml pipet;

. The sample is drawn up into the calibrated limb of the viscometer. and is held there for 9 minutes before timing flow from upper to lower mark;

. The sample is released against the stopwatch, and

time of flow for the sample is recorded.

The viscosity in seconds is the time it takes the sample to flow between the marks.

The results of the tests for the six samples of oxidized starch were as follows:

TABLE III iscositt In second High pll Lott SAMPH- pH Ill 32 Ao Prime Grade Wheat Starch Oxidized Co Large Granule Wheat Starch Oxidized Do Small (iranulc Wheat Starch ()xidircd LL. 7 grams ofthe dry product 1 Jllsecond flovl time under the dL\L nhed conditions for regular starch "'ie 5 grams of the dr product 3| seconds a noted (Ch/Starch) it can be seen from Table III that a difference in halogen oxidation rate efficiency exists. The large granule starch product (Sample Co) of the invention was thinned by oxidation considerably more than either prime grade wheat starch (Sample A0) or the small granule starch by-product of the invention (Sample Do). The lower viscosity number indicates a lower vis cosity for the sample tested. and Sample Co was lowest at both pH 2.53.0 and pH 8.5. Sample Do retained a relatively high viscosity. even after oxidation. indicating relatively little thinning effect from the oxidation procedure. with a little change noted from changing the pH. The granule size apparently has an effect on the halogen oxidation rate, with the large granule starch (Sample Co) showing the best rate.

PROCESS AND PROCESS EQUIPMENT a) diameter. cylindrical section hl height. cylindrical ction cl diameter. feed aperture dl diameter. vortex finder cl length. vortex finder inside hydrocyelonc l') diameter. discharge aperture gl apex angle A type Doxie Impurity Eliminator having the above dimensions is available from Dorr-Oliver. lnc.. Stamford. Connecticut and has been used successfully in the system of the invention. It is contemplated that various changes in dimensions could be made provided that other compensating steps are taken. For example. if a higher feed pressure were used. it may be possible to use somewhat larger hydrocyclones. A smaller hydrocyclone would be expected to perform better at decreased feed pressure. lt is also possible to use different sized hydrocyclones for first pass separation than those used for the second pass separation step For best results. it has been found that at least two hydrocyclones l and 2 should be arranged in series. as

\llt)\\ti in l'l l. 7. so that input line lcnters the feed aperture o1 liytlrocyclone l to supply prime grade liquid starch slurrn cctl under pressure to the natural vortex flow llt\ltlc .lie liydrocyclone l. The preferred feed solids level which has gi\en best results is at about 7.5"Be. The feed to hydrocyclone l must be prime grade native colloid wheat starch slurry which is sub stantially free of fiber and gluten. As mentioned previously. the system does not operate well on rcslurried prime grade starch granules which have been dried. There is apparently a change in hydration capacity caused by the drying process. and which hinders the separation effect in the hydrocyclones.

The prime grade. native colloid wheat starch slurry provided as feed to the system may be the product of the well known batter process for producing wheat starch. Such a system is described at page 58 of Whistler et al.. Vol. II. op. cit.. and various other publications. including US. Pat. Nos. 2.453.310, 2.504.962. 2.5 [7.149 and 2.537.81 l. There are many variations of the starch milling process. but the important requirements of the feed to the process system of the invention is that it be in native colloid slurry form. containing only prime grade starch. and that it be substantially free of other matter, such as salts, gluten and fiber which tend to interfere with the separating effect of the hydrocyclones. lf the feed slurry is not at the desired solids level. it is either concentrated or diluted as necessary to bring the solids level to about 7.5 Be 13.55% solids. d.b. Pump 4 provides a feed pressure input of about 150-210 psig. This input feed pressure can be increased. with some improvement in large granule concentration noted with increasing feed pressure. Avail ability of equipment, electrical power costs and other similar consideratinos. including desired yield will influence the extent of increase in pump capacity considered feasible.

The overflow output line 5 carries the small granule by-product of the invention to a DeLaval centrifuge 6. where it is dewatered. The small granule product can then be filtered. washed and then dried in the conventional manner. The small granule product contains starch granules which are substantially all smaller than 12 microns.

The underflow output line 7 from the hydrocyclone l is maintained at a solids level of about l9.0l9.6 Be. (34.31% solids. d.b.) This partially separated slurry is then diluted with water to a solids level of about 7.4-7.6 Be. (13.55% solids d.b.) ahead of second pass feed pump 8. The partially separated. diluted slurry is then pumped as input feed to hydrocyelones 2 through second pass input feed line 9. The input feed pressure is maintained at about l50-2l0 psig. with the prefer enee being fora feed pressure of about 200 psig.

The separation process is repeated in the hydrocyclones 2 to produce an overflow through lines l0 which includes substantially all the remaining starch granules less than l2 microns in size. The undcrflow output from hydrocyeloncs 2 is throttled to maintain the underflow density at about l9.0l9.6 Be. (34.3]71 solids, db).

This underllow output slurry from hydrocyelones 2 contains the large granule starch product of the invention. trom which substantially all the small granules have been removed. The large granule output slurry is collected through line ll. and then "finished" in the normal manner. The fini hing teps may include coarse screening. filtering. and drying. 'l he dry cake may be to ground in a Jeffrey mill. taking care to avoid fragment ing the granules.

The dried. large granule starch product of the in\ention appears substantially as shown in HG. 4 of the drawings. As can be seen. this product comprises sub stantially more large granules than the starting prime grade starch shown in FIG. 2 of the drawing. Also. comparison of FIG. 4 to FIG. 3 shows very clearly the striking difference in granule size between the small granule by-product and the large granule product.

The large granule product was further modified as follows:

CROSS-LINKING PROCESS The urea-formaldehyde-water (UF-) mixture having a parts ratio of 29:59: l5. in the order listed above, was used to cross-link the large granule starch product. The starch product was first slurried to a solids level of about 2023 Be. and the pH was adjusted to about 2.8-3.0 with concentrated HCl. The UF-85 cross-linker is then added to the slurry at about 0.7 percent by weight level and the reaction is allowed to proceed at room temperature for three hours. The pH is then adjusted to 5.56.0 with a 14-18 percent by weight solu' tion of soda ash. The slurry is then diluted to l2l5 Be. and dried. The cross-linked. large granule starch product made as above exhibited greater heat resistance than the comparable large granule product with out cross-linking. These cross-linked large granules re tained their shapes with no pasting after being heated at C. for 40 minutes. as shown in FIG. 6 of the drawings. This added heat resistance makes the cross-linked product useful for additional duplicating paper coating operations which include higher temperature steps that destroy the unmodified large granules.

OXlDlZED. CROSS-LINKED PRODUCT lhl (cl Large granuleoxidwed at cross linked adiusted pH wheat starch acid pH. at 3 using Ul- 85" to 5.5

using NaOCl (1.6 by WL. with Slurry .04: dsb.) N.i

lClslarch l Time 2 hrs. lime 3 hrs.

After cross-linking. the product is filtered. washed. and dried. Tests were conducted in making carbonless duplicating paper comparing the oxidized. cross-linked large granule product with arrowroot starch. the large granule. unmodified product, and with the large granule. oxidized product, such as the sample designated Sample Co. described earlier. The samples were used to coat the duplicating paper in a process in which the starch particles are subjected to sustained heating of about l50F. for about two hours. The respective samples were then observed for smudge" values. which is an optical observation of the extent of protection dur ing handling given by the starch particles to the microencapsulatcd ink particles in the paper coating. The ox idl/ed cross-linked large granule product described above performed satiductoril in these comparisons. and just as well as arrowroot. and is an ideal replace lhe method ot the invention Wlll give a large granule product which will compare to arrowroot in particle sl7cs as follows:

'lABlli l\' Luge (imnulc Wheat Starch Arrowrnot B) By \tt i Si/e wt. '/1 Size Ii 28 microns. and larger 25 30 microns. and larger 50 24 microns. and lLlTgLl 50 26 microns. and larger 75 20 microns. and larger 75 21 nncrons. and larger Various modes of carrying out the invention are bement for it. lieved to be within the scope of the following claims.

We claim: SUMMARY 1. A large granule cereal starch product obtained by The new large granule cereal starch product of the wet process separation from a native colloid slurry of invention. the small granule cereal starch by-product. bimodal granule starch selected from the group of and the modified large granule cereal starch product of wheat. barley and rye starches. at least about 22% of the invention are each useful in a number of special apthe total number of granules of said large granule ceplications in which cereal starch was not formerly conreal starch being at least 22 microns in size. about 997r sidered useful. The invention allows the use ofa plentiby weight of the granules are at least [2 microns in size. ful cereal starch such as wheat, barley or rye as a resaid starch being substantially free of other matter. and placement for the very scarce and expensive arrowroot 35 having been obtained by hydrocyclone separation di starch. especially in applications such as anti-offset lirectly from native colloid starch slurry from which subthography powders and carbonless duplicating paper stantially all ofgluten. fiber and other matter have been where the granule shape and size is important. removed.

Wheat. barely and rye starches have a natural distri- 2. The product of claim 1, in which at least 55% by bution of larger granules ranging from about mi- 30 weight of the granules are larger than 22 microns. cronsin size and small granules below l0microns,with 3. The product of claim I. in which the starch is few intermediate size granules. The large granules of prime grade wheat starch derived from a continuous these particular native cereal starches are uniformly wet batter process to obtain a native colloid starch round in shape. similar in size and appearance to an slurry. and is then subjected to hydrocyclonic separarowroot starch granules. The annual world production tion while yet in native colloid slurry. for these cereal grains from which these starches are 4. The starch product of claim I, in which the starch made is approximately: granules have been acid-modified.

Wheat l 1.342.000 bushels i970) 5. A large granule cereal starch product obtained by Barley 5,088,000,000 bushels (I970) wet process separation from a native colloid slurry of a Rye 1,500,000.000 bushels I966) bimodal granule starch selected from the group consist- Arrowroot is scarce, and much more expensive than ing of wheat, barley. or rye starches. said starch prodthe above starches. so the product and process of the uct comprising at least 99 percent by weight granules at invention provides an inexpensive and readily abunleast 12 microns in size, and being substantially free of dant substitute for arrowroot starch. The invention is water soluble carbohydrates. and containing less than made possible by the important discovery that it is necabout 0.0l percent ether extractible fats. said starch essary to perform the separation process using hydrohaving been obtained by hydrocyclone separation dicyclones on native colloid prime grade starch slurry rectly from native colloid starch slurry from which subwhich is free as possible of other matter such as salt. stantially all of gluten. fiber. and other matter has been fiber and gluten. and which has not been dried subseremoved. quent to the wet milling process. It has also been found. 6. The product of claim 5. in which at least about 22 especially when wheat starch is being processed. that percent ofthc total number of granules are 22 microns the separation process should be carried out through a in size. or larger. first pass hydrocyclone and a second pass hydrocyclone 7. The product of claim 6, which has been oxidized. utilizing the partially separated underflow from the first 8. The process of making a large granuie cereal pass hydrocyclone as the feed input to the second hystarch selected from the group consisting ofwheat. bar drocyclonc. ley. and rye. the steps comprising first obtaining a na The hydrocycloncs are carefully selected for all ditive colloid starch slurry substantially free of gluten, mensions. and have no moving parts. Separation is a fiber and other matter than subjecting said native colfunction of solids level (density) of the imput feed to loid starch slurry to hydrocyclonic separation in a first the hydrocyclones. the input pressure. and the throthydrocyclone. collecting the partially separated large tling balance of the overflow and underflow. For the granule underflow slurry from said first hydrocyelone, most desirable size separation which will give a product subjecting sid partially separated large granule underhaving at least 55 percent by weight of its granules flow slurry to hydrocyclonic separation in a second hylarger than 22 microns. the input solids level ofthe feed 5 drocyclone. and collecting the large granule underflow to the first and second pass hydrocyclones should be maintained at about 7.5 Be. and the liquid pump pressure in the feed line should be maintained at about l72-2l0 psig.

from said second hydrocyclone to obtain a large granule cereal starch having at least 22 percent granules as large as 22 microns. and substantially free of matter other than unbroken starch granules.

9. lhc process ol claim 8. including the step ol cot lecting the small granule starch ovcrllovv liom said tiist and second hydrocyclones.

10. The process oi claim 8. in which the native col loid slurry is prime grade \vhcat starch slurry substan tially free of salt. fiber. gluten and all foreign materials 11. The process of claim 8. in which the starch is wheat starch made by the continuous batter process. and the feed slurry to said first and second hydrocy clones is maintained at about 7.5Be.

l2. The process of claim 11. in which the first and second hydroeyclones have substantially the following dimensions:

a) diameter. cylindrical section llll" b) height. cylindrical section li/EZ" c) diameter. teed aperture ilo" d) diameter. vortex finder lilo-l" cl length. vortex finder inside hydrocyclone 'Jltt" t) diameter. discharge aperture .lfill" gl apex angle In.

13. The process of claim 12, in which the partially separated underflow from said first hydrocyclone is diluted with water to provide a partially separated input feed slurry to said second hydrocyclorie at a feed solids level of about 7.5Be.. and about 13.55% solids. dry basis.

14. The process of claim 12. in which the hydraulic feed pressure to said first and second hydrocyclones is maintained in the range of about [SO-2H) pounds per square inch gage.

[5. The process of claim 14. in which the input feed pressure to said first hydrocyclone is maintained at about 200 pounds per square inch above atmospheric pressure.

16. A large granule cereal starch product obtained by wet process separation from a native colloid slurry of bimodal granule starch selected from the group consisting of wheat. barley or rye starches. said improved starch product having a sub-sieve value substantially higher than I08 microns. said starch having been obtained by hydrocyclone separation directly from native colloid starch slurry.

(ill

20 i7. The product oltlaiin lb. llii\llt. a sub t iluc less than about Ztltl. but substanttallx higher than lll a 18. 'l he product ol claini 16. ha\ ing a sub=sie\ c \aluc ol at least about l). l.

l9. llic product ol claim 16. in \\hich the subsicvc value is obtained on said large granule product from which substantially all ol the gluten. i'ibcr and other matter has been removed.

20. A large granule cereal starch selected from the group consisting of wheat. barley and r \c starches. at least about 22 percent ot the total number oi granules being at least 22 microns in size. said starch having a sab sieve value substantially greater than that of prime grade wheat starch. and said starch having been obtained by hydrocyclone separation directly from native colloid starch slurry from which substantially all gluten fiber and other non starch matter have been removed.

21. The large granule starch ofclaim 20. in which the subsieve value is substantially more than about l0.8 microns.

22. The large granule starch 01' claim 20. in which the subsieve value is more than about l9] microns.

23. The large granule starch ol claim 20. in which the subsieve value is less than about 20.8. but substantially more than about 10.8.

24. A large granule cereal starch product selected from the group consisting of wheat. barley or rye starches. said starch comprising at least 22 percent granules which are 22 microns in size or larger. and having a sub-sieve value higher than that oi prime grade bimodal cereal starch ol the selected type. tested under comparable conditions.

25. The large granule cereal starch product of claim 24. in which the sub-sieve value is higher than |().8.

26. The starch product of claim 25 in which the cereal starch is wheat.

27. The starch product ofelaim 26. in which the subsieve value is considerably higher than 10.8.

28. The starch product of claim 27. in which the subsieve value is at least four units higher than the subsieve value for prime grade bimodal wheat starch granules which are subjected to the same sub-sieve tests.

UNITED STATES PATENT AND TRADEMARK OFFICE CERTIFICATE OF CORRECTION PATENT NO.

DATED INVENTOR(S) Column Column Column Column Column Column Column Column Column Column Column Column Column Column Column Column Column Column Column Column August 26, 1975 John L. Bond, Saul Rogols, John W. Salter rt is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

17, l7, l7, l8, l8,

[SEAL] line line line line line line line line line line line line line line line line line line line line as, 12, 23, 26, 33, 67, 22, 3a, 50, 64, so,

for for for for for for for for for for for for for for for for for for for for "barely" read barley "from about" read ---above--- "11,342,000" read ---11,342,000,o00--- "than" read ---then--- "aid" read ---aaid--- Signed and Scaled this fourth Day of May 1976 RUTH C. MASON c. MA Awning 0mm asruu. DANN mnmissimu'r nj'lun-"m and Trademarks 

1. A LARGE GRANULE CEREAL STARCH PRODUCT OBTAINED BY WET PROCESS SEPERATION FROM A NATIVE COLLOID SLURRY OF BIMODAL GRANULE STARCH SELECTED FROM THE GROUP OF WHEAT, BARLEY AND RYE STARCHES, AT LEAST ABOUT 22% OF THE TOTAL NUMBER OF GRANULES OF SAID LARGE GRANULE CEREAL STARCH BEING AT LEAST 22 MICRONS IN SIZE, ABOUT 99% BY WEIGHT OF THE GRANULE ARE OF OTHER 12 MICRONS IN SIZE, SAID STARCH BEING SUBSTANTIALLY FREE OF OTHER MATTER, AND HVING BEEN OBTAINED BY HYDROCYCLONE SEPARATION DIRECTLY FROM NATIVE COLLOID STARCH SLURRY FROM WHICH SUBSTANTIALLY ALL OF GLUTEN, FIBER AND OTHER MATTER HAVE BEEN REMOVED.
 2. The product of claim 1, in which at least 55% by weight of the granules are larger than 22 microns.
 3. The product of claim 1, in which the starch is prime grade wheat starch derived from a continuous wet batter process to obtain a native colloid starch slurry, and is then subjected to hydrocyclonic separation while yet in native colloid slurry.
 4. The starch product of claim 1, in which the starch granules have been acid-modified.
 5. A large granule cereal starch product obtained by wet process separation from a native colloid slurry of a bimodal granule starch selected from the group consisting of wheat, barley, or rye starches, said starch product comprising at least 99 percent by weight granules at least 12 microns in size, and being substantially free of water soluble carbohydrates, and containing less than about 0.01 percent ether extractible fats, said starch having been obtained by hydrocyclone separation directly from native colloid starch slurry from which substantially all of gluten, fiber, and other matter has been removed.
 6. The product of claim 5, in which at least about 22 percent of the total number of granules are 22 microns in size, or larger.
 7. The product of claim 6, which has been oxidized.
 8. The process of making a large granule cereal starch selected from the group consisting of wheat, barley, and rye, the steps comprising first obtaining a native colloid starch slurry substantially free of gluten, fiber and other matter than subjecting said native colloid starch slurry to hydrocyclonic separation in a first hydrocyclone, collecting the partially separated large granule underflow slurry from said first hydrocyclone, subjecting sid partially separated large granule underflow slurry to hydrocyclonic separation in a second hydrocyclone, and collecting the large granule underflow from said second hydrocyclone to obtain a large granule cereal starch having at least 22 percent granules as large as 22 microns, and substantially free of matter other than unbroken starch granules.
 9. The process of claim 8, including the step of collecting the small granule starch overflow from said first and second hydrocyclones.
 10. The process of claim 8, in which the native colloid slurry is prime grade wheat starch slurry substantially free of salt, fiber, gluten and all foreign materials.
 11. The process of claim 8, in which the starch is wheat starch made by the continuous batter process, and the feed slurry to said first and second hydrocyclones is maintained at about 7.5*Be.
 12. The process of claim 11, in which the first and second hydrocyclones have substantially the following dimensions:
 13. The process of claim 12, in which the partially separated underflow from said first hydrocyclone is diluted with water to provide a partially separated input feed slurry to said second hydrocyclone at a feed solids level of about 7.5*Be., and about 13.55% solids, dry basis.
 14. The process of claim 12, in which the hydraulic feed pressure to said first and second hydrocyclones is maintained in the range of about 150-210 pounds per square inch gage.
 15. The process of claim 14, in which the input feed pressure to said first hydrocyclone is maintained at about 200 pounds per square inch above atmospheric pressure.
 16. A large granule cereal starch product obtained by wet process separation from a native colloid slurry of bimodal granule starch selected from the group consisting of wheat, barley or rye starches, said improved starch product having a sub-sieve value substantially higher than 10.8 microns, said starch having been obtained by hydrocyclone separation directly from native colloid starch slurry.
 17. The product of claim 16, having a sub-sieve value less than about 20.8, but substantially higher than 10.8.
 18. The product of claim 16, having a sub-sieve value of at least about 19.1.
 19. The product of claim 16, in which the sub-sieve value is obtained on said large granule product from which substantially all of the gluten, fiber and other matter has been removed.
 20. A large granule cereal starch selected from the group consisting of wheat, barley and rye starches, at least about 22 percent of the total number of granules being at least 22 microns in size, said starch having a sub-sieve value substantially greater than that of prime grade wheat starch, and said starch having been obtained by hydrocyclone separation directly from native colloid starch slurry from which substantially all gluten fiber and other non-starch matter have been removed.
 21. The large granule starch of claim 20, in which the subsieve value is substantially more than about 10.8 microns.
 22. The large granule starch of claim 20, in which the subsieve value is more than about 19.1 microns.
 23. The large granule starch of claim 20, in which the subsieve value is less than about 20.8, but substantially more than about 10.8.
 24. A large granule cereal starch product selected from the group consisting of wheat, barley or rye starches, said starch comprising at least 22 percent granules which are 22 microns in size or larger, and having a sub-sieve value higher than that of prime grade bimodal cereal starch of the selected type, tested under comparable conditions.
 25. The large granule cereal starch product of claim 24, in which the sub-sieve value is higher than 10.8.
 26. The starch product of claim 25 in which the cereal starch is wheat.
 27. The starch product of claim 26, in which the sub-sieve value is considerably higher than 10.8.
 28. The starch product of claim 27, in which the sub-sieve value is at least four units higher than the sub-sieve value for prime grade bimodal wheat starch granules which are subjected to the same sub-sieve tests. 